Ion-molecule reactions and collision-activated dissociation of C4H 4 +. isomers: A case study in the use of the MS3 capabilities of a pentaquadrupole mass spectrometer

  • Brian J. Shay
  • Marcos N. Eberlin
  • R. Graham Cooks
  • Chrysostomos Wesdemiotis
Articles

Abstract

Isomeric C4H 4 +. radical cations vinylacetylene (a), butatriene (b), methylene cyclopropene (c), and the nonaromatic cyclobutadiene (d), generated, respectively, from the neutral precursors 3-butyn-1-ol (1), 1,4-dichloro-2-butyne (2), benzene (3), and 7,8-benzotricyclo [4.2.2.02,5]deca-3,7,9-triene (4), undergo diagnostically different ion-molecule reactions with allene, isoprene, furan, and thiophene. It is speculated that adducts are generated by [2 + 2] cycloadditions with the first reagent and [4 + 2] Dials-Alder cycloadditions with isoprene, furan, and thiophene. The initially formed cycloaddition adducts fragment rapidly, isomerize, or undergo further addition of neutral reagent to yield a complex set of products. With a pentaquadrupole mass spectrometer, MS3 experiments that employ three stages of ion mass analysis are used to help elucidate the ion-molecule reactions and to distinguish the isomeric C4H 4 +. ions. Among these experiments, the reaction intermediate spectrum reveals the nature of the intermediates connecting the reactant to a selected product while the sequential product spectrum provides mechanistic and structural information on the adducts and other ion-molecule products. The unique combination of ion-molecule reactions with collision-activated dissociation employed here provides valuable information on the chemistry of ionized cyclobutadiene, including its proclivity to undergo [2 + 2] and [4 + 2] cyc1oadditions.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.(a)
    Gross, M. L.; Lin, P. H.; Franklin, S. J. Anal. Chem. 1972, 44, 974; (b) Ferrer-Correia, A, J. V.; Jennings, K. R; Sen Sharma, D. K. Org. Mass Spectrom. 1976, 11, 876; (c) Budzikiewicz, H.; Busker, E. Tetrahedron 1980, 36, 255; (d) Keough, T. Anal, Chem. 1982, 54, 2540; (e) Staley, R. H.; Corderman, R. R; Foster, M, 5.; Beauchamp, J. L. J. Am, Chem. Soc. 1974, 96, 1260; (f) Bowers, M. T., Ed.; Gas Phase Ion Chemistry; Academic Press: Orlando, 1979, vol 2. (g) Harrison, A. G., Ed.; Chemical Ionization Mass Spectrometry; CRC Press: Boca Raton, FL, 1983; (h) Witlneben, D.; Brützmacher, H. F. Int. J. Mass Spectrom. Ion Proc. 1990, 100, 545.CrossRefGoogle Scholar
  2. 2.
    Lias, S. G.; Liebman, J. F.; Levin, R. D. J. Phys. Chem. Ref Data 1984, 13, 695.CrossRefGoogle Scholar
  3. 3.(a)
    De Ruy, C. H.; Gronert, S.; Mullin, A.; Bierbaum, V. M. J. Am. Chem. Soc. 1990, 112, 8650; (b) Paulino, J. S.; Squires, R R. J. Am. Chem. Soc. 1991, 113, 1845.CrossRefGoogle Scholar
  4. 4.(a)
    Kenttamaa, H. I.; Cooks, R. G. J. Am, Chem. Sac, 1989, 111, 4122; (b) Kenttämaa, H. I.; Pachuta, R. R.; Rothwell, A. P.; Cooks, R. G. J. Am. Chem. Soc. 1989, 111, 1654; (c) Prome, D.; Prome, J. c.;Stahl, D. Org. Mass Specirom. 1985, 8, 525; (d) Kinter, M. T.; Bursey, M. M, J. Am. Chem. Soc. 1986, 108, 1797; (e) Jalonen, J. J. Chem. Soc, Chem. Commun, 1985, 872; (f) Freeden, D. A.; Russell, D. H. J. Am. Chem. Soc. 1986, 108, 1860; (g) Gross, M, L. Adv. Mass Spectrom. 1989, 11a 792; (h) Tabet, J. C.; Einhorn, J. Org. Mass Spectrom. 1985, 20, 310; (i) Bouchoux, G.; Hoppilliard, Y.; Jaudon, P.; Pechine, J. M. Rapid Commun. Mass Spectrom. 1987, 2, 20; (j) Eberlin, M. N.; Majumdar, T. K.; Cooks, R. G. J. Am. Chem. Soc. in press.CrossRefGoogle Scholar
  5. 5. (a)
    Dymerski, P. P.; McLafferty, F. W. J. Am. Chem. Soc. 1976, 6070; (b) Lay, J. 0.; Gross, M, L. J. Am. Chem. Soc. 1983, 105, 3445.Google Scholar
  6. 6.(a)
    Schwartz, J. C.; Schey, K. L.; Cooks, R. G. Int. J. Mass Spectrom, Ion Proc. 1990, 101, 1; (b) Morrison, J. D.; Stanney, D. A.; Tedder, J. Proc, 34th Am. Soc. Mass Spectrom. Conf. Mass Spectrom. Allied Topics, Cincinnati, 1986, p 222; (c) Beaugrand, G.; Devant, G.; Iaouen, D.; Rolando, C. H. Int. J. Mass Spectrom. Ion Proc. in press; (d) Mestdagh, H,; Morin, N.; Rolando, C. H.; Beaugrand, c.; De Maack, F. Proc. 34th Am. Soc. Mass Spectrom. Conf Mass Spectrom. Allied Topics, Cincinnati, 1986, p 799,CrossRefGoogle Scholar
  7. 7.
    Schwartz, J. C., Wade, A. P., Enke, C. G.; Cooks, R. G. Anal, Chem. 1990, 62, 1809.CrossRefGoogle Scholar
  8. 8.
    Burinski, D. J.; Cooks, R. G.; Chess, E. K.; Gross, M. L. Anal, Chem. 1982, 54, 295.CrossRefGoogle Scholar
  9. 9.
    Tomer, K. B.; Guenat, C. K; Deterding, L. J. Anal. Chem. 1988, 60, 2232.CrossRefGoogle Scholar
  10. 10.
    Louris, J. N.; Wright, L. G.; Cooks, R. G.; Schoen, A. G. Anal. Chem. 1985, 57, 2918.CrossRefGoogle Scholar
  11. 11.
    Orlando, R; Murphy, C.; Fenselau, C.; Hansen, G.; Cotler, R. J. Anal. Chem. 1990, 62, 125.CrossRefGoogle Scholar
  12. 12.
    O’Lear, J. R.; Wright, L. G.; Louris, J. N., Cooks, R. G. Org. Mass Spectrom. 1987, 22, 348.CrossRefGoogle Scholar
  13. 13.
    Dolnikowski, G. C., Health, T. G.; Watson, J. T.; Scrivens, J. H.; Rolando, C. H. J. Am. Soc. Mass Spectrom. 1990, 1, 481.CrossRefGoogle Scholar
  14. 14.
    Majumdar, T.; Eberlin, M. N.; Cooks, R. G.; Green, M. M.; Muñoz, B.; Reidy, M. P. J. Am. Soc. Mass Spectrom. 1991, 2, 130.CrossRefGoogle Scholar
  15. 15.
    Schey, K. L.; Schwartz, J. C; Cooks, R. G, Rapid Commun. Mass Spectrom. 1989, 3, 305.CrossRefGoogle Scholar
  16. 16.(a)
    Rosenstock, H. M.; Larkins, J. T.; Walker, J. A. Int. J. Mass Spectrom. Ion Phys. 1973, 11, 309; (b) Rosenstock. H. M.; McCulloh, K. E. Int. J. Mass Spectrom. Ion Phys. 1977, 25, 327.CrossRefGoogle Scholar
  17. 17.
    Baer, T.; Willett, G. D.; Smith, D.; Phillips, J. S. J. Chem. Phys. 1979, 70, 4076.CrossRefGoogle Scholar
  18. 18.(a)
    Ausloos, P. J. Am. Chem. Soc. 1981, 103, 3931; (b) Lifshitz, C; Gibson, D.; Levson, K.; Doran, I. Int. J. Mass Spectrom. Ion Phys. 1981, 40, 157.CrossRefGoogle Scholar
  19. 19.
    Wagner-Redeker, W.; Hues, A. J.; Kemper, P. R.; Bowers, M. T. J. Am. Chem. Soc. 1983, 105, 5719.CrossRefGoogle Scholar
  20. 20.
    Ray Jr., J.C; Danis, P.O.; McLafferty, F. W.; Carpenter, B. K. J. Am. Chem. Soc. 1987, 109, 4408.CrossRefGoogle Scholar
  21. 21.
    Wesdemiotis, C.; Zhang, M. Y.; McLafferty, F. W. Org. Mass Spectrom. 1991, 26, 671.CrossRefGoogle Scholar
  22. 22.
    Zhang, M. Y.; Wesdemiotis, C; Marchetti, M.; Danis, P. O.; Ray Jr., J. C., Carpenter, B. K.; Mclafferty, F. W. J. Am. Chem. Soc. 1989, 111, 8341.CrossRefGoogle Scholar
  23. 23.(a)
    Mclafferty, F. W. Science 1990, 247, 925; (b) McLafferty, F. W.; Wesdemiolis, C. Org. Mass Spectrom. 1989, 24, 663; (c) Holmes, J. L. Adv. Mass Spectrom. 1989, 11a, 53; (d) Wesdemiotis, c.; McLafferty, F. W. Chem. Rev. 1987, 87, 485; (e) Terlouw, J. K.; Schwarz, H. Angew. Chem. Int. Ed. Engl. 1987, 26, 805; (f) Holmes, J. L. Org. Mass Spectrom. 1985, 20, 169; (g) Danis, P.O.; Wesdemiotis, C. McLafferty, F. W. J. Am. Chem. Soc. 1983, 105, 7454.CrossRefGoogle Scholar
  24. 24.
    Zhang, M. Y.; Carpenter, B. K.; McLafferty, F. W., J. Am. Chem. Soc. 1991, 113, 94–99.Google Scholar
  25. 25.
    Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. D.; Mallard, W. G. J. Phys. Chem. Ref. Data 1988, 17, suppl 1.Google Scholar
  26. 26.
    Staley, S. W.; Norden, T. D. J. Am. Chem. Soc. 1989, 111, 445.CrossRefGoogle Scholar
  27. 27.
    Kriete, J.; Miinzel, N.; Schweig, A.; Specht, H. Chem. Phys. Lett. 1986, 24, 140.Google Scholar
  28. 28.
    Hess Jr., B. A.; Allen, W. D.; Michalsky, D.; Schaed, L. T.; Schaefer III, H. F. J. Am, Chem. Soc. 1987, 109, 1615.CrossRefGoogle Scholar
  29. 29.(a)
    Groenewold, G. S.; Gross, M. L. J. Am. Chem. Soc. 1984, 106, 6575; (b) Holman, R. W.; Rozenboom, M. D.; Gross, M. L. Tetrehedron 1986, 42, 6235, and references therein.CrossRefGoogle Scholar
  30. 30.(a)
    Gassman, P. G.; Singleton, D. A. J. Am. Chem. Soc. 1984, 106, 7993; (b) Gassman, P. G.; Singleton, D. A.; Wilwerding, J. J.; Chavan, S. P. J. Am. Chem. Soc. 1987, 109, 2182,CrossRefGoogle Scholar
  31. 31.(a)
    Bauld, N. L.; Bellville, D. J.; Harirchian, B.; Lorenz, K. T.; Pabon Jr., P. A.; Reynolds, D. W.; Wirth, D. D.; Chiou, H. S.; Marsh, B. K. Acc. Chem. Res. 1987, 20, 371; (b) Kim, T.; Pye, J.; Bauld, N. L. J. Am. Chem. Soc. 1990, 112, 6285.CrossRefGoogle Scholar
  32. 32.
    Schwartz, J.C. Ph.D. dissertation; Purdue University, West Lafayette, IN, July 1989.Google Scholar
  33. 33.
    Dawson, P. H., Ed. Quadrupole Mass Spectrometry and Its Applications; Elsevier: New York, 1976.Google Scholar
  34. 34.(a)
    Carpenter, B. K. J. Am. Chem. Soc. 1983, 105, 1700; (b) Ray Jr., J. C Ph.D. dissertation; Cornell University, Ithaca, NY, August 1986. 35. Bowers, M. T.; Elleman, D. D.; O’Malley, R. M.; Jennings, K. R. J. Phys. Chem. 1970, 74, 2583.CrossRefGoogle Scholar
  35. 36.
    Jarrold, M. F.; lilies, A. J.; Kirchner, N. J.; Bowers, M. T. Org. Mass Spectrom. 1983, 18, 388.CrossRefGoogle Scholar
  36. 37.
    van der Hart, W. J. Org. Mass Spectrom. 1988, 23, 187.CrossRefGoogle Scholar
  37. 38.
    March, J. Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 3rd ed.; Wiley: New York, 1985.Google Scholar
  38. 39.
    McLafferty, F. W.; Stauffer, D. B. The Wiley-NBS Registry of Mass Spectra Data; Wiley: New York, 1989, vol 1, P 73.Google Scholar
  39. 40.
    Johnstone, R. A. W., Ed. Mass Spectrometry; Chemical Society: London, 1979, vol 5, p 277.Google Scholar

Copyright information

© American Society for Mass Spectrometry 1992

Authors and Affiliations

  • Brian J. Shay
    • 3
  • Marcos N. Eberlin
    • 3
    • 2
  • R. Graham Cooks
    • 3
  • Chrysostomos Wesdemiotis
    • 1
  1. 1.Department of ChemistryUniversity of AkronAkronUSA
  2. 2.Universidade Estadual de CampinasCampinasBrazil
  3. 3.Department of ChemistryPurdue UniversityWest Lafayette

Personalised recommendations